FR2671352A1 - NOVEL CATIONIC COPOLYMERS, NEW EMULSIONS AND THEIR APPLICATION - Google Patents

Abstract

Cationic copolymers insoluble in water based on acryl amide and a cationic monomer of general formula (I) (CF DRAWING IN BOPI) in which R and R1, identical or different, represent a hydrogen atom or a group methyl, X represents an oxygen atom or an NH radical and n represents 2 or 3, containing in molar proportions of 5 to 30% of cationic units, and crosslinked with 50 to 100 ppm of bisacrylamidoacetic acid relative to the weight of the copolymer, emulsions containing them and application to the thickening of a household softener.

Description

The present invention relates to novel cationic copolymers,

  new emulsions and their application. Cationic emulsions are widely used in modern household softeners which typically contain from 2 to 25% by weight of a water-insoluble quaternary ammonium associated with one or more

  stabilizing nonionic emulsifiers.

  The viscosity of household softeners is usually less than 100 m Pa s at 20 C, but the market is demanding softeners more viscous: about 200 m Pa S or more, to give consumers the impression of smoothness that they associate with a better

  softening and softening power.

  Conventional thickeners: derivatives of cellulose, xanthan gum, guar gum, non-crosslinked or slightly crosslinked water-soluble polymers, optionally presented in self-reversible water-in-oil emulsion, etc. are not entirely satisfactory because, either they are in the form of powder difficult to dissolve perfectly, either they are incompatible with the cationic dispersion, or they provide thickened media with a more or less pronounced spinning, or finally, they lead to thickened media unstable over time: demixing, formation of mottling, and or gold deposits, the applicant has discovered new derivatives, used in particular in the form of emulsions, obviating these drawbacks and further having the following advantages: possibility of fluid presentation fluid, easy to handle and implement, sensitivity low shear emulsion, good storage stability e: weak sedimentation and release, weak odor sui generis not altering the perfume of the finished product,

rheology little or not shooting.

  This is why the present application relates to new cationic copolymers insoluble in water, characterized in that they are based on acrylamide and a cationic monomer of general formula (I) Q / CH 3 CH 2 C CO X (CH 2) f N CH 3 Cl (I)

R R 1

  in which R and R 1, which may be identical or different, represent a hydrogen atom or a methyl group, X represents an oxygen atom or an NH radical and n represents 2 or 3, containing in molar proportions from 5 to 30 % of cationic units, and crosslinked with from 50 to 100 ppm of bisacrylamidoacetic acid relative to the weight of the copolymer. The subject of the invention is in particular the copolymers described above, characterized in that said copolymers are crosslinked with approximately 100 ppm of bisacrylamidoacetic acid, hereinafter referred to as ABAA relative to the weight of copolymer. The invention is more particularly intended to copolymers as defined above in which the monomer of general formula (I) is either dimethylaminoethyl acrylate salified with hydrochloric acid, hereinafter referred to as CHA, or dimethylaminoethyl acrylate quaternized with chloride methyl,

  hereinafter referred to as CMA, or finally methacryl chloride

  amidopropyltrimethylammonium, hereinafter referred to as MAPTAC.

  Advantageously, the cationic monomer is CMA. Among these latter products, the invention particularly relates to those containing either an AAM-CMA copolymer, 92-8 in molar proportions, preferably cross-linked with 100 ppm of ABAA, or a copolymer AAM-CMA, 80-20 in molar proportions, preferably also cross-linked with 100 ppm

  ABAA AAM is acrylamide.

  The cationic copolymers according to the present invention can be obtained from the corresponding monomers and crosslinking agent, by radical polymerization, in water-in-oil suspension in the presence of one or more stabilizing agents and one or more free radical generators. at a temperature of between + 10 ° C. and + 1000 ° C. The crosslinked cationic copolymer is insoluble in water but swellable with water.

  advantageously presented in the form of an emulsion

  reversible water in oil It is then present in the dispersed aqueous phase which it represents advantageously

  about 35 to 45% of its weight.

  This is why the present application also relates to a self-reversible water-in-oil emulsion, characterized in that it contains a copolymer

  cationic as defined above.

  The continuous oil phase of the emulsion is mainly constituted by a liquid oil at ambient temperature and having a boiling point

  between 150 and 375 C, preferably commercial.

  Advantageously, this oil is either a paraffin

  Linear C 10 -C 13, a paraffinic-naphthenic oil

  with a boiling point of 200 to 350 C. A water-insoluble, water-in-oil emulsion of a water-insoluble cationic copolymer generally contains one or more HLB emulsifiers (hydrophilic-lipophilic balance) greater than 8 in the phase aqueous solution and one or more HLB emulsifiers of less than 5 in

the oily phase.

  The continuous oily phase represents

  typically 20 to 35% by weight of the total weight of the emulsion

  and usually contains 1 to 4% by weight of emul-

  sifiants. Among the emulsifiers with an HLB value of less than 5, mention may be made of sorbitan fatty esters, such as sorbitan monooleate or sorbitan sesquioleate. Among the emulsifiers of HLB value greater than 8, mention may be made of ethoxylated nonylphenols with from 6 to 12 molecules of ethylene oxide, oleocetyl alcohols

  ethoxylated with from 10 to 12 molecules of ethylene oxide.

  The emulsions of the present invention will preferably contain: about 30 to 50% water,

  about 25 to 35% of cationic copolymers

  some 20 to 35% of oil,

  3% to about 8 t of several

sifiants.

  The emulsions according to the present invention can be obtained from commercial products by known methods such as those described by the Applicant in French Patent No. 2507606 in which the initiator system used is replaced by the one described in French Patent No. 2529895 as taught in the prior art, emulsifiers of HLB value greater than 8 are

  introduced into the emulsion at the end of the polymer reaction.

  tion, and their purpose is to stabilize

  on the one hand, and make it self-reversible on the other.

  Moreover, it is known that CMA or CHA are cationic monomers that are very sensitive to hydrolysis, it is therefore necessary, when they are used in a polymerization reaction, to adjust the pH of the phase

aqueous between 3 and 6.

  The copolymers according to the present invention, especially in emulsion form, have excellent thickening properties of aqueous dispersions containing insoluble or poorly water-soluble quaternary ammoniums, such as household softeners. Their use in the form of emulsions above described in such dispersions at weight doses of between 0.05 and 1% relative to the total weight of the dispersion, leads to thickened dispersions, not very sensitive to shear,

stable in storage, little shooting.

  Therefore, the present application finally relates to the application of a copolymer or an emulsion

  self-reversible, as described above, to the thickening

of a household softener.

  The following examples illustrate the invention

without limiting it.

EXAMPLES 1-9

  The thickening power of various products of the invention in emulsion form, E, and their influence on the stability of a commercial household softener, designated hereinafter, has been investigated. This study is carried out by addition of E in S followed by homogenisation by

stirring for 15 minutes.

  In Table I, the values of viscosities found as a function of the temperature and storage time of fabric softener S in which a thickener E has been introduced at the concentration, C, are indicated. The notation OK means that the product does not have a solid deposit Viscosities are

  Brookfield viscosities determined at 200 C with a screw

  Brookfield RVT, at speed 20 and with the mobile

  2, and they are expressed in m Pa s.

  The characteristics of the emulsion E used

  molar composition, weight concentration in copoly-

  designated parent, Ce, crosslinking rate expressed in ppm relative to the total weight of the copolymer, Brookfield viscosity of E at 200 C and its appearance after three months of storage at C, designated As, are mentioned in the second part

of the Board.

  The comparison of Examples 1 to 3 shows that

  the product containing the most cationic emulsion E (ex.

1) is the least stable.

  Furthermore, emulsions E containing a cationic monomer salified with hydrochloric acid

  Inducing corrosion problems Emulsions containing a quaternized cationic monomer will therefore be preferred.

  Comparison of examples 4 (counter

  example) and shows that a crosslinked polymer insoluble in

  the water thickens more and gives more stable products (ex.

  ), and the comparison of Examples 6 to 8 shows that a

  highly cationic thickener (ex 8) leads to a

  softener having a lower viscosity stability

than that of Examples 6 and 7.

EXAMPLES 10-16

  In order to assess the storage stability of the cationic dispersions thickened with a product according to the invention, we determined the Brookfield viscosity at C (speed 20 rpm, mobile 2) expressed in m Pa S of a household softener treated with various products according to the invention at the indicated dose expressed as a weight percentage of product as such, firstly as a function of time, and secondly, after a spinning of 15 and

  minutes at 20 C, at a speed of 5200 revolutions per minute.

  We have also studied the behavior of this thickened cationic dispersion with a product according to the invention when it is subjected to a centrifugation of 15,000 revolutions per minute, 13000 G, for 30 minutes, at C. The stability was then assessed visually according to the rate of release and it was rated from 1 to 5, from very good 1 to very bad 5 The results of these

  different tests are given in Tables II and III.

  The results obtained show that a dispersal

  cationic cation treated with an emulsion based on a cationic copolymer weakly crosslinked, therefore outside the scope of the present invention, (ex 14) has a poor stability to centrifugation whereas the cationic dispersions treated with an emulsion according to the present invention simultaneously exhibit a

  good stability in storage, turbining and centrifugation

gation.

TABLE I

  Witness EXAMPLES Witness 2 3 4 5 6 7 8

EXAMPLES

  S. Concoentration C, 0.25% 0.15% 0.15% 0.3% 0.1 OS% 0.1% 0.07% 0.22% Viscosity 86 214 265 245 232 242 244 219 234 270 Vi $ cosil apras Viscosity after80 185 234 199 215 217 205 200 180 * 2 months at 20 ° C Viscosity after 2 months at 40 'C100 164 210 190 180 170 190 175 140 Aspect after 2 seconds 2' OK strlures OK OK striations OK OK OK OK 2 months to 20 '0 Appearance after *

OK OK OK OK OK OK OK OK

  2 months at 40 ° C Composition (molar) CHA 30 / AAMM 70 CHA 15 / AA MM 85 CHA 8 / AAM 92 OMA 20 / MAAM 70 OMA 30 / MM 70 OMA 8 / MM 92 OMA 20 / MM 80 OMA 55 / MM 45 MM 92 MAPTAC 8

28.4 3% 3004%

  Ce 3 275 3% 30% 275% 28.8% 30% 33 288% 30.4% Crosslinking rate 50 ppm 100 ppm 100 ppm 100 ppm 100 ppm 100 ppm 98 ppm 500 pp 520 pp Viscosity do E at 20 ° C600 1000 1230 1130 300 300 1000 1500 500 620 As OK OK OK OK OK OK OK "'1 t O

TABLE II

  Examples 10 1 12 Nature's control E ex 1 ex 6 ex 7 Concentration 0.3% 0.21% 0.15% Viscosity at 20 ° C time O 212 187 209 66 after 1 h 212 194 215 after 2 h 210 200 217 after 4 h 212 200 220 after 48 h 212 205 220 65 Viscosity after spinning for 15 min 204 180 194 29 for 30 mrin 207 184 197 29

TABLE III

  Stability after centrifugation Examples 13 14 15 16 Nature control of E ex 1 ex 4 ex 6 ex 7 O Concentration 0.2% 0.35% 0.06% 0, 2% O Assessment 2 4 1 1 1

EXAMPLE 17

  300 g of bidistilled water, 6.16 g of citric acid with one molecule of water are mixed at room temperature with stirring, 232.7 g (3.27 moles) of crystallized acrylamide, 72.65 g. g of an aqueous solution containing 76% by weight of CMA, ie 0.285 mol, 10 g of a 0.25 aqueous solution,

  % by weight of ABABAA, 0.288 g of azobisamidine hydrochloride

  dinopropane, 0.92 g of formic acid and 0.5 g of a 40% by weight aqueous solution of sodium salt of diethylenetriaminopentaacetic acid. The pH of this solution is then adjusted to pH = 3.5. with a few drops of potash lye then we introduce water up to

  obtaining a total weight of 700 g.

  Moreover, stirring is mixed 19 g

  of sorbitan sesquioleate in 241 g of a

  paraffinic-naphthenic mercury having a boiling point of 300 to 350 ° C. In a polymerization reactor, the aqueous solution prepared previously in the oil phase obtained above is cast while stirring, and the dispersion is then emulsified with a turbine during minutes and the emulsion obtained is then carefully deoxygenated by sparging with nitrogen, for 30 minutes at 15 ° C.

  then introduced into this emulsion 0.0432 g of hydro-

  cumene peroxide and 0.0576 g of thionyl chloride The polymerization reaction starts immediately, the temperature of the reaction medium reaches 90 ° C. in 15 minutes, the mixture is left standing for 1 hour at this temperature with stirring and then the emulsion is cooled to 50 ° C. 9 g of ethoxylated oleocetyl alcohol are introduced with 10 molecules of ethylene oxide and 11 g of oleocetyl alcohol ethoxylated with 12 ethylene oxide molecules, and then the emulsion is cooled to room temperature. an emulsion containing by weight 28.8% of an AAM-CMA copolymer, 92-8 in molar proportions, crosslinked with 100 ppm relative to the weight of this bisacrylamidoacetic acid copolymer, having a Brookfield viscosity

  1000 m Pa S determined at 20 C with a Brookfield VRT model viscometer, equipped with the mobile 2, at speed 20. This emulsion is stable over time; after two months of storage at 20 ° C., it shows no salting out or sedimentation.

  This emulsion was used in Example 6.

Claims (8)

  1 cationic copolymers insoluble in water, characterized in that they are based on acrylamide and a cationic monomer of general formula (I) G 1 _ / CH 3   CH 2 C CO X (CH 2) N N CH 3 Cl G (I) R R 1   in which R and R 1, identical or different, represent   a hydrogen atom or a methyl group, X represents an oxygen atom or an NH radical and n represents 2 or 3, containing in molar proportions of 5 to% of cationic units, and crosslinked with from 50 to 100 ppm of bisacrylamidoacetic acid relative to the weight of the copolymer   2 cationic copolymers according to the   cation 1 characterized in that the copolymer is   crosslinked with about 100 ppm of bisacrylamidoacetic acid   as compared to the weight of copolymer   3 Cationic Copolymers According to the Claim   1 or 2 characterized in that the copolymer is dimethylaminoethyl acrylate quaternized with chloride of methyl.   4 Cationic Copolymers according to one   any of claims 1 to 3 characterized in that   the copolymer is a copolymer of acrylamide and dimethylaminoethyl acrylate quaternized with methyl chloride   containing in molar proportions 8% of cationic   c. Self-reversible emulsion, water in oil,   characterized in that it contains a cationic copolymer that according to claim 1.   6 Self-reversible emulsion, water in oil,   characterized in that it contains a cationic copolymer according to claim 2 or 3.   7 Self-reversible emulsion, water in oil,   characterized in that it contains a cationic copolymer according to claim 4.   8 Self-reversible emulsion, water in oil,   characterized in that it contains a cationic copolymer according to claim 5.   9 Application of a copolymer according to one   any of claims 1 to 4 to the thickening of a domestic softener.   Application of a self-reverting emulsion   according to any one of claims 5 to 8 to   the thickening of a household softener.